KR20060046734A - Producing method for thin metal laminated body - Google Patents

Abstract

Irrespective of the kind of base material, the manufacturing method of the thin film metal laminated body which can obtain the thin film metal laminated body which has excellent adhesiveness between a thin film metal layer and a base material in a short time is provided.

As a manufacturing method of the thin film metal laminated body on a base material, it is characterized by including following process (1)-(3).

(1) step of preparing the base material

(2) A step of injecting a flame of a fuel gas containing a silicon-containing compound or spraying a gaseous product of the silicon-containing compound through a heat source of 400 ° C. or higher on the substrate surface;

(3 ') Process of forming base layer which becomes ultraviolet curable resin

(3) Process of forming thin metal layer by metal ion reduction treatment, for example, silver mirror reaction

Thin film metal laminate, silicon-containing compound, spray treatment, ion reduction reaction

Description

Producing method for thin metal laminated body

1 is a manufacturing flowchart of the thin film metal laminate of the present invention.

2 is a manufacturing flowchart of another thin film metal laminate of the present invention.

FIG.3 (a)-(c) is a figure provided in order to demonstrate the laminated body obtained by the manufacturing method of a thin film metal laminated body.

It is a figure provided in order to demonstrate a flame-type surface modification apparatus.

It is a figure provided in order to demonstrate a heat source surface treatment apparatus.

It is a figure provided in order to demonstrate a needle-type surface treatment apparatus.

It is a figure provided in order to demonstrate the reduction treatment apparatus of a metal ion.

It is a figure provided in order to demonstrate the spray gun as a reduction apparatus of a metal ion.

It is a figure provided in order to demonstrate the spray apparatus as a reduction apparatus of a metal ion.

10 is a view provided to explain the play tool.

11 is a manufacturing flowchart of a conventional thin film metal laminate.

Explanation of the sign

10, 10 '： Flame type surface modification device

12: Storage tank (1st storage tank) of a silicon containing compound

14 silicon-containing compound

16: heating means

18 ： pressure gauge

22 ： Mixing room

24 ： Transfer section

25 ： heat source

27 ： Storage tank of carrier gas

28 ： Pressure gauge

32 ： injection part

35 ： second heat source

37 ： Second storage tank of carrier gas

40: mention

80, 80 ', 80' ': laminated body

82: mention

84 ： Surface treatment layer (silica layer)

86 ： Thin film metal layer

87 ： Protective layer (protective film)

100 ： heat source surface treatment apparatus

200: needle type surface treatment apparatus

300 ： spray gun

400, 400 ': Reduction treatment apparatus of metal ions

500 ： Play Tool

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thin film metal laminate, and in particular, a thin film metal having excellent adhesion between a substrate (substrate with base layer, which is the same below) and the thin film metal layer. The manufacturing method of a laminated body is related.

Conventionally, when forming a thin-film metal layer using a silver mirror reaction, as shown in the manufacturing flowchart of FIG. 11, in addition to the primer application | coating shown by process sequence 4 and the undercoat application | coating shown by process sequence 6, process sequence 8 and process sequence 10 Alternatively, as shown in step 13, it has been considered essential to perform a plurality of activation treatments or stabilization treatments using a specific activation treatment agent (a hydrochloric acid solution of a first tin ion or a ferridium ion) or a stabilizer (for example, See Patent Document 1).

However, in order to perform a plurality of activation treatments or stabilization treatments using a specific activation treatment agent or stabilizer, a long time is required, and the activation treatment effect or stabilization treatment effect is likely to be insufficient. Since the adhesiveness is still insufficient, the thin film metal layer is easily corroded or cracked due to hydrochloric acid which is easily peeled off from the substrate or used.

In addition to the above-described thin film metal layer, the conventional thin film metal layer has a high selectivity with respect to the substrate type, and it was difficult to form a thin film metal layer uniformly and firmly with respect to polypropylene, polyester, or the like.

On the other hand, the inventor of the present invention efficiently burns even when the silicon-containing compound containing a silane atom is used in a relatively large amount when spraying a flame which is a fuel gas containing a silicon-containing compound to the substrate to perform a silicate treatment. The surface modification method which makes it easy to carry out and which can uniformly and fully modify surfaces, such as a base material, is proposed (for example, refer patent document 2).

However, it was not known that the value of the volume resistivity (surface resistance) can be adjusted by performing such a silicate salt treatment, and the adhesion effect as a thin film metal layer or its base layer formed by the reduction reaction of metal ions using the same, It was not known that it could be used to increase the stabilization effect of the electroconductivity.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2004-190061 (Patent Claims)

[Patent Document 2] WO03 / 069017 Publication (claim)

Therefore, the inventors of the present invention, as a result of diligent effort, perform a predetermined silicate salt treatment or the like before forming a thin film metal layer by a reduction reaction of metal ions represented by a silver mirror reaction or the like on a substrate. Irrespective of whether it was possible to obtain the thin film metal laminated body which has the outstanding adhesiveness between a thin film metal layer and a base material in a short time, it came to complete this invention.

Therefore, the objective of this invention is providing the manufacturing method of the thin film metal laminated body which can obtain the outstanding adhesiveness between a thin film metal layer and a base material by a quick, simple and easy preprocessing method.

ADVANTAGE OF THE INVENTION According to this invention, as a manufacturing method of the thin film metal laminated body on a base material, the manufacturing method of the thin film metal laminated body characterized by including the following process (1)-(3) is provided, and the above-mentioned problem can be solved. have.

(1) step of preparing the base material

(2) A step of injecting a flame of a fuel gas containing a silicon-containing compound or spraying a gaseous substance of the silicon-containing compound through a heat source of 400 ° C. or higher on the substrate surface;

(3) Process of Forming Thin Film Metal Layer by Reduction of Metal Ions

Moreover, in implementing the manufacturing method of the thin film metal laminated body of this invention, it is preferable to make thickness of a thin film metal layer into the value within 0.01-100 micrometers range.

Moreover, in implementing the manufacturing method of the thin film metal laminated body of this invention, it is preferable that a thin film metal layer contains at least 1 among gold, silver, copper, nickel, and aluminum as a main component, especially silver.

Moreover, in implementing the manufacturing method of the thin film metal laminated body of this invention, it is preferable to make the wetness index (measurement temperature 25 degreeC) of the base material surface of a process (2) into the value within 40-80 dyn / cm range.

Moreover, in implementing the manufacturing method of the thin film metal laminated body of this invention, it is preferable to make the volume resistivity of the surface of the base material of a process (2) into the value within the range of 1 * 10 <^4> -1 * 10 <^{10> (} ohm) * cm.

Furthermore, in implementing the manufacturing method of the thin film metal laminated body of this invention, the process of forming a base layer (3 ') between process (2) and process (3) is further provided, and a base material and a thin film metal layer It is preferable to form a base layer between and.

Moreover, in implementing the manufacturing method of the thin film metal laminated body of this invention, it is preferable to make the injection time of a flame or gaseous form into the value within 0.1 second-100 second per unit area (100 cm <2>).

Moreover, in implementing the manufacturing method of the thin film metal laminated body of this invention, it is preferable that a base material contains at least 1 among a glass material, a polycarbonate resin, a polyolefin resin, a polyester resin, and a polyimide resin as a main component.

Moreover, in implementing the manufacturing method of the thin film metal laminated body of this invention, it is preferable to provide the process of forming a protective layer (4) further after a process (3), and to form a protective layer on the surface of a thin film metal layer. Do.

Moreover, in implementing the manufacturing method of the thin film metal laminated body of this invention, it is preferable to form either a base layer, a protective layer, or either one by ultraviolet curable resin.

Moreover, in implementing the manufacturing method of the thin film metal laminated body of this invention, it is preferable to form a thin film metal laminated body as a part of a play tool, an electrical appliance, a vehicle, a mechanical component, a tool, furniture, or an ornament.

According to the method for producing a thin film metal laminate of the present invention, before forming the thin film metal layer by a reduction reaction of metal ions such as silver mirror reaction, a flame of fuel gas containing a silicon-containing compound is sprayed or Or by spray-processing the gaseous substance of a silicon containing compound through the heat source more than predetermined temperature, the outstanding adhesiveness between a thin film metal layer and a base material can be obtained.

In other words, the silicon-containing compound rapidly reacts with pyrolysis by a flame or a heat source to react to form a silica layer having a concave-convex shape and a predetermined volume resistivity on the surface of the substrate, thereby exerting a function as a special conductive base layer. . As a result, excellent adhesiveness can be obtained between the thin film metal layer and the substrate.

In addition, since the silica layer having a concave-convex shape formed on the surface of the substrate and having a predetermined volume resistivity can exhibit a predetermined smoothing function, a more uniform and smooth thin film metal layer or a base layer thereof can be formed.

On the other hand, according to the manufacturing method of the thin film metal laminated body of this invention, since it can abbreviate | omit suitably also about several surface activation treatment, the ultraviolet-ray hardening pretreatment, etc., continuous and rapid manufacture can be performed and as a result, thin film metal The laminate can also be produced at low cost.

Moreover, according to the manufacturing method of the thin film metal laminated body of this invention, predetermined electroconductivity, light reflection characteristic, decorativeness, durability, etc. can be obtained by making thickness of a thin film metal layer into a predetermined thickness.

Moreover, according to the manufacturing method of the thin film metal laminated body of this invention, when a thin film metal layer contains at least one in silver, copper, etc. as a main component, predetermined | prescribed electroconductivity and light reflection characteristic can be obtained in a thin film metal layer, and a thin film metal layer It can also stabilize the resistance of.

On the other hand, since the combination of silver nitrate and the reducing agent conventionally used for the reduction reaction of metal ions can be used as it is, and since it is excellent in electroconductivity and a light reflection characteristic, it is more preferable to contain silver as a main component of a thin film metal layer.

Moreover, according to the manufacturing method of the thin film metal laminated body of this invention, in the process (2), between the thin film metal layer and a base material by adjusting the wetness index (measurement temperature of 25 degreeC) of the surface of a base material to the value of a predetermined range. Further excellent adhesiveness can be obtained stably.

Moreover, according to the manufacturing method of the thin film metal laminated body of this invention, in the process (2), by adjusting the volume resistivity of the surface of a base material to the value of a predetermined range, the function as a special conductivity improvement layer can be exhibited. Therefore, more excellent adhesiveness can be obtained between the thin film metal layer and the substrate, and the resistance of the thin film metal layer can be stabilized.

Moreover, by adding a coloring agent, electroconductive particle, etc. to a base layer, the decorative effect, external appearance, and resistance of a thin film metal layer can be stabilized more.

Moreover, according to the manufacturing method of the thin film metal laminated body of this invention, by providing the process (3 ') which forms a specific base layer further, it is further excellent between the base layer provided in the lower part of the thin film metal layer, and a base material. Adhesion can be obtained.

In addition, according to the method for producing a thin film metal laminate of the present invention, by controlling the injection time of a predetermined flame or gaseous product to a value within a predetermined time range per unit area, it is possible to easily control the volume resistivity and the wettability index of the substrate. You can do it.

Moreover, according to the manufacturing method of the thin film metal laminated body of this invention, predetermined | prescribed heat resistance can be obtained when a base material contains a glass material, a polycarbonate resin, a polyimide resin, etc. as a main component. Moreover, predetermined | prescribed flexibility and light weight can be acquired when a base material contains polyester resin, a polyolefin resin, etc. as a main component.

Moreover, in implementing the manufacturing method of the thin film metal laminated body of this invention, the durability of a thin film metal laminated body can be remarkably improved by providing process (4) further and forming a protective layer on the surface of a thin film metal layer. . Moreover, by adding a coloring agent, electroconductive particle, etc. to a protective layer, the decorative effect and external appearance of a thin film metal laminated body can be improved, or the resistance of a thin film metal layer can be stabilized more.

Moreover, in implementing the manufacturing method of the thin film metal laminated body of this invention, by forming a thin film metal laminated body as a part of a play tool, etc., decoration of the play tool etc. can be performed easily and quickly.

On the other hand, the play tool etc. have many plating formation parts, and it can obtain the advantage that it can manufacture extremely economically by replacing it with the thin film metal laminated body of this invention.

This invention is a manufacturing method of the thin film metal laminated body on a base material, As shown to FIG. 1 or FIG. 2, manufacture of the thin film metal laminated body characterized by including following process (1)-(3). It is a way.

(1) Process of preparing base material (Hereinafter, it may be called preparation process.)

(2) Process of spray-injecting flame of fuel gas containing silicon-containing compound or gaseous substance of silicon-containing compound through heat source of 400 ° C or higher (hereinafter referred to as surface treatment step) There is a case.)

(3) Process of forming thin film metal layer by reduction reaction of metal ion (Hereinafter, it may be called metal ion reduction process.)

1-10, the aspect of this invention is divided into a preparation process, a surface treatment process, a reduction process of a metal ion, and these inspection process which is these next processes, and demonstrates concretely.

On the other hand, the manufacturing method of the thin film metal laminate shown in FIG. 1 is the simplest and easiest manufacturing flowchart using the reduction reaction of metal ion, and the manufacturing method of the thin film metal laminate shown in FIG. 2 is a thin film metal lamination which includes formation of a base layer. A manufacturing flowchart of the sieve.

3 (a) to 3 (c) show examples of aspects of the thin film metal laminates 80, 80 ', and 80' 'provided with the thin film metal layer 86 obtained by the present invention, respectively. 3A is an example in which a specific surface treatment layer (silica layer) 84 and a thin film metal layer 86 are provided on a base material 82, and FIG. The thin film metal laminate 80 ′ shown in FIG. 2 is an example in which a specific surface treatment layer 84, a base layer 85, and a thin film metal layer 86 are provided on a base material 82, and the thin film shown in FIG. 3 (c). The metal laminate 80 ″ is an example in which a specific surface treatment layer 84, a thin film metal layer 86, and a protective layer 87 are provided on a substrate 82.

4 to 6 are views showing the outlines of the surface treatment apparatuses 10, 10 ', and 50, respectively, and FIG. 7 shows the surface treatment apparatus 10 and the metal ion reduction treatment apparatus 400. FIG. It is a figure which shows the outline | summary of the manufacturing line of the thin film metal laminated body containing this. FIG. 8 is a view showing one type of spray gun 300 used in the metal ion reduction treatment apparatus 400, and FIG. 9 is a reduction treatment apparatus 400 'for such a spray type metal ion. ) Is a schematic diagram, and FIG. 10: is a figure which shows the outline of the play tool 500 as an example of use of the thin film metal laminated body 80. As shown in FIG.

1. Preparation process

Although the kind in particular of the base material prepared in the preparation process of this invention is not restrict | limited, For example, glass, a metal, a ceramic, resin, etc. are mentioned as a constituent material.

And as glass which comprises a base material, soda glass (alkali glass), an alkali free glass, low alkali glass, quartz glass, borosilicate glass, phosphate glass, lead glass, colored glass, electroconductive glass, etc. are mentioned specifically ,.

For example, the alkali free glass had high volume resistivity as it is, and even if surface activation treatment was performed, it was difficult to form a uniform thin film metal layer by reduction treatment of metal ions. Therefore, the thin film metal layer which is excellent in adhesiveness can be formed by performing the silicication flame treatment of a silicon containing compound, etc. with respect to the surface of an alkali free glass, and then performing a reduction process of predetermined metal ion.

Moreover, as a metal which comprises a base material, single type | mold or 2 or more types of knitting, such as gold, silver, copper, aluminum, iron, magnesium, stainless steel, nickel, chromium, tungsten, zinc, tin, and lead, are mentioned.

For example, although aluminum is widely used as a light weight metal, it is easy to form an oxide film on the surface, and it showed the problem that the reduction process of a metal ion cannot be performed as it is. Therefore, the thin film metal layer excellent in adhesiveness can be formed by performing the silicication flame treatment of a silicon containing compound, etc. with respect to an aluminum surface, and then performing a reduction process of a metal ion.

In addition, magnesium is widely used in cases such as personal computers as a recyclable metal member, but since the surface smoothness is lacking, the thin film metal layer is easily peeled off even if sputtering or reduction of metal ions is performed. Seemed. Therefore, the thin film metal layer which is excellent in adhesiveness can be formed by performing the silicication flame treatment of a silicon containing compound, etc. with respect to a magnesium surface, and then reducing metal ions.

As the ceramic constituting the base material, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, zinc oxide, indium oxide, tin oxide, magnesium oxide, calcium oxide, aluminum nitride, silicon nitride, titanium nitride, zirconium nitride, zinc nitride And one type or two or more types of knitting such as indium nitride, tin nitride, magnesium nitride, calcium nitride or bricks made of these ceramic materials, fireproof walls, containers, ceramics, ceramic base materials, and the like.

For example, ceramic substrates made of aluminum oxide or the like are widely used as heat resistant and lightweight circuit boards. However, since the thermal conductivity is good and it is difficult to keep the surface temperature at a predetermined temperature, sputtering and reduction of metal ions are required. Even if a process was performed, the problem that the thin film metal layer peels easily was shown. Therefore, the thin film metal layer which is excellent in adhesiveness can be formed by performing the silicate salt process using a silicon containing compound, etc. with respect to the surface of a ceramic base material, and then reducing metal ions.

As the resin constituting the substrate, polyethylene resin (high density polyethylene, medium density polyethylene, low density polyethylene, high pressure polyethylene, medium pressure polyethylene, low pressure polyethylene, linear low density polyethylene, branched low density polyethylene, high pressure linear low density polyethylene, ultra ( Solid polyethylene, crosslinked polyethylene), polypropylene resin, modified polypropylene resin, polymethylpentene resin, norbornene resin, polyester resin, polycarbonate resin, polyethersulfone resin, polyacrylic resin, polyether ether ketone Resin, polysulfone resin, polystyrene resin, polyamide resin, polyimide resin, polyamideimide resin, phenol resin, urea resin, vinyl chloride resin, ABS resin, polyphenylene sulfide resin, ethylene-tetrafluoroethylene copolymer, poly Vinyl fluoride resin, tetraflu Low ethylene-perfluoro ether copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, polytetrafluoroethylene resins, polyvinylidene fluoride resins, polytrifluorochloroethylene resins, ethylene-trifluorochloroethylene copolymers, and the like. Can be mentioned.

Therefore, by performing a silicate salt treatment using a silicon-containing compound or the like on a base material containing these resins as a main component, a predetermined metal ion reduction treatment can be performed to form a thin film metal layer excellent in adhesion, thereby removing the thin film metal layer. This can be effectively prevented.

Further, the shape of the base material used in the present invention is not particularly limited. For example, planar structures such as a plate shape, a sheet shape, a film shape, a tape shape, a sheet shape, a panel shape, and a string shape may be used. It may be partially or have three dimensions such as a container shape, a cylindrical shape, a columnar shape, a spherical shape, a block shape, a tube shape, a pipe shape, an uneven shape, a film shape, a fiber shape, a fabric shape, and a bundle shape. It may have a structure.

Furthermore, the above-mentioned composites of glass, metal, ceramic, resin and the like may be used. For example, according to the present invention, a thin film metal layer can be formed by performing a silicate salt treatment using a silicon-containing compound or the like on a fibrous glass or carbon fiber, followed by a reduction treatment of metal ions. Therefore, predetermined conductive composites can be obtained by uniformly dispersing such conductive fibers in matrix resins such as epoxy resins and polyester resins. That is, it is possible to exhibit excellent mechanical strength, heat resistance, electromagnetic shielding effect, etc. as a conductive composite having FRP or CFRP as the core material.

2. Surface Treatment Process

Subsequently, as shown in the manufacturing flowchart shown in FIG. 1 and FIG. 2, the silicate salt process etc. which used the silicon containing compound on the base material are performed as a surface treatment process.

(1) silicon-containing compounds

It is preferable to make the boiling point (under atmospheric pressure) of the silicon containing compound used in the surface treatment process of this invention into the value within 10-200 degreeC range.

The reason is that when the boiling point of such a silicon-containing compound is a value of less than 10 ° C, volatility may be intense and handling may be difficult. On the other hand, when the boiling point of such a silicon-containing compound exceeds 200 ° C., the mixing property with air may be lowered, resulting in uneven surface modification of the substrate or it may be difficult to sustain the modifying effect for a long time.

Therefore, it is more preferable to make the boiling point of such a silicon containing compound into the value within 15-180 degreeC range, and it is still more preferable to set it as the value within 20-120 degreeC range.

In addition, although the boiling point of such a silicon containing compound can also be adjusted by restrict | limiting the structure of a silicon containing compound itself, In addition, using the alkylsilane compound with a relatively low boiling point, the alkoxysilane compound etc. with a comparatively high boiling point, etc. are used suitably. I can adjust it.

Moreover, it does not restrict | limit especially about the kind of silicon containing compound, For example, an alkylsilane compound, an alkoxysilane compound, etc. are mentioned.

Suitable examples of such alkylsilane compounds or alkoxysilane compounds include tetramethylsilane, tetraethylsilane, dimethyldichlorosilane, dimethyldiphenylsilane, diethyldichlorosilane, diethyldiphenylsilane, methyltrichlorosilane, methyltriphenylsilane, dimethyl Diethylsilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, diphenyldimethoxysilane, diphenyldidie One type single or 2 types or more combinations, such as a methoxysilane, a trichloromethoxysilane, a trichloroethoxysilane, a triphenyl methoxysilane, and a triphenylethoxysilane, are mentioned.

Moreover, it is more preferable to have at least one among a nitrogen atom, a halogen atom, a vinyl group, and an amino group in a molecule | numerator or a molecular terminal in a silicon containing compound.

More specifically, hexamethyldisilazane (boiling point: 126 ° C), vinyltrimethoxysilane (boiling point: 123 ° C), vinyltriethoxysilane (boiling point: 161 ° C), trifluoropropyltrimethoxysilane ( Boiling point: 144 ° C), trifluoropropyltrichlorosilane (boiling point: 113-114 ° C), 3-aminopropyltrimethoxysilane (boiling point: 215 ° C), 3-aminopropyltriethoxysilane (boiling point: 217 ° C ), Hexamethyldisiloxane (boiling point: 100-101 ° C), and 3-chloropropyltrimethoxysilane (boiling point: 196 ° C) are preferably at least one compound.

The reason for this is that such a silicon-containing compound improves the mixing properties with the carrier gas, forms a granular material (silica layer) on the surface of the substrate, makes the modification more uniform, and the relationship between boiling point and the like. This is because such a silicon-containing compound tends to remain partly on the surface of the base material, so that better adhesion can be obtained between the base material and the thin film metal layer.

(2) flame

In the surface treatment process of this invention, as shown in FIG. 4, the silicon-containing compound 14 is sprayed uniformly with respect to the base material 40, and the flame is made to thermally decompose and oxidize the silicon-containing compound 14 easily. It is preferable to use.

That is, it is preferable to mix a predetermined amount of silicon-containing compound in the fuel gas, to burn it, to make it a flame, and to blow it onto the surface of the substrate.

Therefore, it is preferable to make flame temperature into the value within the range of 500-1,500 degreeC.

This is because when the temperature of such a flame reaches a value below 500 ° C, it may be difficult to effectively prevent incomplete combustion of the silicon-containing compound. On the other hand, when the temperature of such a flame exceeds 1,500 degreeC, the base material of surface modification may thermally deform or thermally deteriorate, and the kind of base material which can be used may be excessively restrict | limited. Therefore, it is preferable to make the temperature of a flame into the value within the range of 550-1,200 degreeC, and it is more preferable to set it as the value within the range of less than 600-900 degreeC.

In addition, when using a flame, it is preferable to make the addition amount of a silicon containing compound into the value within the range of 1 * 10 <^{-10> -10} mol% when the total amount of fuel gas is 100 mol%.

This is because when the addition amount of such a silicon-containing compound becomes a value of less than 1 × 10 ^-10 mol%, the modifying effect on the substrate may not be expressed. On the other hand, when the addition amount of such a silicon containing compound exceeds 10 mol%, the mixing property of a silicon containing compound, air, etc. may fall, and a silicon containing compound may incompletely burn accordingly.

Therefore, when the total amount of the silicon-containing compound is 100 mol%, the amount of the silicon-containing compound is more preferably in the range of 1 × 10 ^-9 to 5 mol%, more preferably in the range of 1 × 10 ^-8 to 1 mol%. It is more preferable to set it as an internal value.

Moreover, since control of such a flame temperature can be made easy, it is preferable to add a flammable gas, a flammable gas, or air etc. (it may be called a flammable gas etc. hereafter) normally in combustion gas.

As such a flammable gas, hydrocarbon, such as propane gas and natural gas, hydrogen, oxygen, etc. are mentioned. On the other hand, when using fuel gas in an aerosol can, it is preferable to use propane gas, compressed air, etc. as such flammable gas.

Moreover, when the total amount of fuel gas is 100 mol%, it is preferable to make content of such a flammable gas etc. into the value within the range of 80-99.9 mol%.

The reason for this is that when the content of such flammable gas or the like is less than 80 mol%, the miscibility with the silicon-containing compound may deteriorate and the silicon-containing compound may be incompletely burned accordingly. On the other hand, when the addition amount of such a flammable gas exceeds 99.9 mol%, the modifying effect with respect to a base material may not be expressed.

Therefore, when the total amount of fuel gas is 100 mol%, it is more preferable to make the addition amount of flammable gas etc. into the value within the range of 85-99 mol%, and it is still more preferable to set it as the value within the range of 90-99 mol%. .

It is also preferable to use a carrier gas in order to easily transport the silicon-containing compound and uniformly mix it in the fuel gas. That is, it is preferable to mix a silicon-containing compound and a carrier gas in advance, transfer it to a predetermined portion, and then mix the flammable gas or the like.

The reason for this is that by using such a carrier gas, even when using a silicon-containing compound having a relatively high molecular weight and difficult to move, it can be easily transported to a predetermined portion and can be mixed uniformly with a flammable gas. Because. That is, by using the carrier gas, not only the handling of the silicon-containing compound becomes easy, but also the combustion is easy, and the surface modification of the substrate can be uniformly and sufficiently performed.

In addition, as the carrier gas, the same kind of gas to be added to the above-described fuel gas can be used. Specifically, hydrocarbons such as air and oxygen, propane gas and natural gas can be cited.

(3) heat source

In addition, in the surface treatment process of this invention, as shown in FIG. 5, while using the heat source 25 for thermally decomposing the silicon-containing compound 14 instead of a flame, the temperature of the heat source 25 is 400-. It is preferable to set it as the value within 2,500 degreeC range.

This is because when the temperature of such a heat source is less than 400 ° C, it may be difficult to thermally decompose the silicon-containing compound to form a granular material having a predetermined shape on the surface of the substrate or the like. On the other hand, when the temperature of such a heat source exceeds 2,500 degreeC, a gaseous substance may be heated excessively, and the base material of surface modification may heat-deform or deteriorate.

Therefore, it is preferable to make the temperature of a heat source into the value within 500-1,800 degreeC, and it is more preferable to set it as the value within 800-1,200 degreeC range.

In addition, the kind of heat source is not particularly limited, but for example, it is preferable to use at least one heating means selected from a laser, a halogen lamp, an infrared lamp, a high frequency coil, an induction heating device, a hot air heater, and a ceramic heater. Do.

For example, by using a laser, the silicon-containing compound can be thermally decomposed by intensively and extremely rapidly heating, for example, the surface treatment of the nano-order patterned semiconductor substrate becomes possible as a base material.

In addition, by using a halogen lamp or an infrared lamp, thermal decomposition of a large amount of silicon-containing compounds becomes possible even at an extremely uniform temperature distribution, and for example, efficient surface treatment of an olefin film or the like as a substrate becomes possible.

Moreover, by using a high frequency coil and an induction heating apparatus, it heats extremely quickly and thermally decomposes a silicon-containing compound, and for example, efficient surface treatment of a base material is attained.

On the other hand, by using a hot air heater or a ceramic heater, for example, a temperature treatment exceeding 2000 ° C. is possible in various sizes from small to large scale, so that the silicon-containing compound is easily thermally decomposed, for example, as a substrate. Efficient surface treatment of a substrate and the like becomes possible.

(4) processing time

In addition, in this invention, it is preferable to make the flushing time (injection time) of the gaseous substance through a flame or a heat source into the value within 0.01 second-100 second per unit area (100 cm <2>).

The reason is that when such injection time becomes a value of less than 0.01 second, the modification effect by a silicon containing compound may not be expressed uniformly. On the other hand, when such injection time exceeds 100 second, the base material of surface modification may thermally deform or deteriorate, and the kind of base material which can be used may be excessively restrict | limited.

Therefore, it is preferable to make such injection time into the value within 0.3-30 second range per unit area (100 cm <2>), and it is more preferable to set it as the value within the range of 0.5-20 second.

(5) Flame Surface Treatment Apparatus

In addition, in the predetermined flame of the present invention, as shown in Fig. 4, the first storage tank 12 for storing the silicon-containing compound 14 and the agent for storing compressed air, flammable gas, or the like. 2 Mixing the storage tank 27, the compressed air, and the silicon-containing compound 14 with fuel, the mixing chamber 22 as fuel gas, the conveying part 24 for conveying the obtained fuel gas, and the flame 34 of the fuel gas being blown out. The flame-type surface treatment apparatus 10 including the injection part 32 for this can be used.

That is, in this example, the heating means 16 which consists of a heating plate connected to a heater, a heating wire, or a heat exchanger is provided in the lower part of the 1st storage tank 12, and usually contains liquid silicon at normal temperature and a normal pressure state. It is comprised so that the compound (14) may be vaporized.

Then, when the substrate 40 is surface treated, the mixing chamber 22 is heated by the heating means 16 in a state where the silicon-containing compound 14 in the first storage tank 12 is heated to a predetermined temperature and vaporized. It is mixed with compressed air, flammable gas, etc. conveyed from the 2nd storage tank 27, and it is set as fuel gas.

On the other hand, since the content of the silicon-containing compound in the fuel gas is extremely important, in order to indirectly control the content of the silicon-containing compound, a pressure gauge (or liquid level gauge) 18 is placed on the first storage tank 12. If the amount of silicon-containing compounds in the first storage tank 12 is reduced by monitoring the vapor pressure (or the amount of silicon-containing compounds) of the silicon-containing compound 14, the silicon-containing compound is stored in the preliminary tank 19. It is preferred to add from.

In addition, the fuel gas delivery unit 24 is generally a tubular structure, and has a mixing chamber 22 for uniformly mixing the silicon-containing compound 14 with compressed air, flammable gas, or the like as the fuel gas as described above. At the same time, the pipe 24 between the mixing chamber 22 and the injector described later includes a plate 30 for controlling the flow rate, a flow meter, or a pressure gauge 28 for controlling the pressure of the fuel gas. have. In the mixing chamber 22, the silicon-containing compound and the compressed air or flammable gas are mixed uniformly, and then a mixing pump or a baffle plate for lengthening the residence time so as to strictly control the flow rate as the fuel gas. It is also preferable to provide (i).

Moreover, the injection part 32 is equipped with the burner for blowing out the flame 34 obtained by burning the fuel gas sent through the piping of the transfer part 24 to the base material 40 to be processed, as shown in FIG. .

The kind of such burner is not particularly limited either, but may be any of a premixed burner, a diffusion burner, a partial premixed burner, a spray burner, an evaporation burner, a pulverized coal burner and the like. In addition, the shape of the burner is not particularly limited, and may be, for example, a fan-shaped constitution as a whole extending toward the tip portion, or may be a generally rectangular and burner having a plurality of injection holes arranged in the horizontal direction.

In addition, it is preferable to arrange | position the injection part 32, ie, the position of a burner, in consideration of the ease of surface modification of the base material 40 which is a to-be-processed object, and the like. For example, it is preferable to arrange | position the injection part 32 along a circular or elliptical shape, or it is also preferable to arrange | position to both sides of the base material 40 which is a to-be-processed object.

On the other hand, it is also preferable to arrange the injection part 32 at a distance of a predetermined distance on one side of the substrate 40 to be processed, and to arrange the injection portion 32 at a distance of a predetermined distance to both sides of the substrate 40 to be processed. desirable.

(6) heat source surface treatment apparatus

In the present invention, the first storage tank 12 for storing the silicon-containing compound 14, as shown in FIG. 5, in blowing gaseous substances including the silicon-containing compound 14 through a heat source. And a second storage tank 27 for storing carrier gas such as compressed air, a heat source (first heat source) 25 for heating carrier gas such as compressed air, vaporized silicon-containing compound 14 and compressed air A mixing chamber 22 for mixing a carrier gas such as a gas into a gaseous substance containing a silicon-containing compound, and a conveying unit 24 for transferring the gaseous substance containing a silicon-containing compound to a predetermined place and a gas containing the silicon-containing compound. It is possible to use a heat source surface modification apparatus 10 ′ including an injection section 32 for blowing the shaped object against the base 40.

Further, when the substrate 40 is surface treated using such a heat source surface modification apparatus 10 ', the silicon-containing compound 14 in the first storage tank 12 is heated to a predetermined temperature by the heating means 16. In the heated and vaporized state, it conveys as shown by arrow C, and mixes with the carrier gas of the heated state introduce | transduced as shown by arrow A, and sets it as a gaseous substance of predetermined temperature. On the other hand, such a heat source surface modification apparatus 10 'can also be equipped with facilities, such as a pressure gauge 18 and a reserve tank, similar to the flame-type surface treatment apparatus 10 mentioned above.

Furthermore, for the precise temperature control of the gaseous product containing the silicon-containing compound, the second heat source 35 is provided separately from the first heat source 25 in the middle of the conveying part 24 and indicated by an arrow B, so as to be in a heated state. It is also preferable to introduce a carrier gas. As the second heat source 35, at least one heating means selected from a laser, a halogen lamp, a ceramic heater, and the like can be used.

That is, in the heat source surface modifying apparatus 10 'having such a configuration, a gaseous substance containing a silicon-containing compound controlled at a predetermined temperature can be flushed with respect to the substrate 40 from all directions, thereby treating the substrate uniformly and sufficiently. You can do it. Moreover, it is not necessary to ignite or extinguish a gaseous substance during surface modification without using a flame, and the burden on a ignition apparatus or the like is small, and the surface treatment apparatus can be easily miniaturized. In addition, there is no need to consider the combustibility of the silicon-containing compound, and the use restrictions on the silicon-containing compound are also reduced.

Moreover, as another heat source surface treatment apparatus, it is also preferable to use the needle-type surface treatment apparatus 50 as shown in FIG. That is, the needle surface treatment apparatus 50 stores the silicon-containing compound 14 and vaporizes the storage tank 12 and the vaporized silicon provided with heating means 16 for heating and vaporizing at a predetermined temperature. Pump (not shown) for conveying the containing compound 14 and the flow plate 66 for controlling the flow rate of the silicon containing compound 14, the conveying pipe 64, and the silicon containing compound 14 connected to it The heat source 58 for heating the heating chamber 56 and the silicon-containing compound 14 to predetermined temperature is provided. In addition, the flow of the silicon containing compound 14 vaporized from the storage tank 12 of a silicon containing compound is shown by arrow A '.

The heating chamber 56 is configured to form a pump 78 for transporting a carrier gas such as compressed air, a flow plate 76 for controlling the flow rate of the carrier gas, and a needle-type surface treatment apparatus 50. Injecting the carrier gas (54a, 54b), the silicon-containing compound (14) heated to a predetermined temperature, and the carrier gas, which are installed around the carrier gas, and blown out of the substrate (40). 60 is provided.

Therefore, in the needle surface treatment apparatus 50 configured as described above, the silicon-containing compound 14 flowing as shown by arrow A 'and the carrier gas flowing as shown by arrow B' are uniformly mixed to a predetermined temperature. As the gaseous substance containing the controlled silicon-containing compound, the substrate 40 can be flushed from all directions.

In addition, with such a needle-type surface treatment apparatus 50, it is possible to concentrate the surface treatment only on a predetermined portion. In addition, the surface treatment apparatus 50 of this type can be easily downsized and can be transported as a portable surface treatment apparatus.

(7) wetness index

In addition, in the surface treatment process of this invention, it is preferable to make the wetness index (measurement temperature of 25 degreeC) of the surface-modified base material into the value within 40-80dyn / cm range.

The reason is that when the wetness index of such a substrate is less than 40 dyn / cm, it may be difficult to form a thin film metal layer having excellent adhesion even if the metal activation treatment is sufficiently performed before the reduction treatment of the metal ions. . On the other hand, if the wettability index of such a substrate exceeds 80 dyn / cm, surface treatment may be performed excessively and the substrate may be thermally deteriorated or fuel may be consumed excessively.

Therefore, in the surface-modified substrate, the wetness index is more preferably in the range of 45 to 78 dyn / cm, more preferably in the range of 50 to 75 dyn / cm.

(8) contact angle

Moreover, in the surface treatment process of this invention, it is preferable to make the contact angle (measurement temperature 25 degreeC) measured using the water of the surface-modified base material to the value within 0.1-30 degree range.

The reason for this is that when the contact angle of such a substrate is less than 0.1 °, surface treatment is excessively performed, and the substrate may be thermally deteriorated or fuel may be excessively consumed. On the other hand, when the contact angle of such a base material exceeds 30 degrees, it may become difficult to form the thin film metal layer excellent in adhesiveness even if metal activation process is fully performed before metal ion reduction treatment.

Therefore, in the surface-modified substrate, it is more preferable to set the contact angle (measurement temperature of 25 ° C) measured using water to a value within the range of 0.5 to 20 °, and more preferably to a value within the range of 1 to 10 °. .

3. Reduction Treatment Process of Metal Ions

Subsequently, as shown in FIG. 1 and FIG. 2, after the surface treatment process (S2, S2 '), a metal ion reduction treatment process (S3, S4') is performed to form a thin film metal layer.

(1) pretreatment process

First, after performing surface treatment process (S2 ') and providing a base layer formation process (S3') as a pretreatment process before performing metal reduction process (S4 '), as shown in FIG. It is preferable to form a base layer on the surface.

The reason for this is that by forming such a base layer, further excellent adhesion between the thin film metal layer and the substrate can be obtained and the electrical resistance of the thin film metal layer can be stabilized.

This is because by forming a patterned base layer such as letters, figures, symbols, etc. on the surface of the substrate, a thin film metal layer patterned corresponding thereto can be formed. That is, by forming a patterned base layer on a predetermined portion of the surface of the substrate and then providing a thin film metal layer on the entire surface to impart further mechanical stimulation or by applying an adhesive tape, the patterned thin film metal layer can be easily and quickly formed. have.

Although the aspect of the base layer formed here is not specifically limited, For example, it is preferable to form the base layer which consists of an ultraviolet curable resin, a thermosetting resin, or a thermoplastic resin.

The reason for this is that by forming the base layer made of such an ultraviolet curable resin, it can be formed quickly without providing a heat treatment step or the like. On the other hand, when forming the base layer which consists of thermosetting resins, an exposure apparatus etc. can be omitted and it can form at low cost. On the other hand, when the base layer made of a thermoplastic resin is formed, curing treatment becomes unnecessary, and excellent storage stability of the coating liquid containing the thermoplastic resin and the like is facilitated in manufacturing management.

In addition, although the kind of ultraviolet curable resin etc. which comprise a base layer are not specifically limited, For example, epoxyacrylate type ultraviolet curable resin, urethane acrylate type ultraviolet curable resin, polyester acrylate type ultraviolet curable resin, etc. It is preferable to use at least one type.

On the other hand, it is preferable that the epoxy acrylate type UV curable coating material is an ultraviolet curable coating material comprised basically from the epoxy acrylate oligomer which may have polar groups, such as a phosphate group, an acrylate monomer, an initiator, and desired resin.

Moreover, it is preferable that a urethane acrylate ultraviolet curable coating material is an ultraviolet curable coating material comprised fundamentally with urethane acrylate oligomer, an acrylate monomer, an initiator, and desired resin.

On the other hand, it is preferable that the polyester acrylate-type ultraviolet curable coating material is an ultraviolet curable coating material comprised basically from polyester acrylate oligomer, an acrylate monomer, an initiator, and desired resin.

Moreover, since the kind of ultraviolet curable resin which forms a base layer has a selectivity with respect to adhesiveness, it is more preferable to consider and consider the kind of silicon-containing compound used for a surface treatment process.

For example, silicon-containing compounds containing nitrogen atoms and halogen atoms in molecules such as hexamethyldisilazane, trifluoropropyltrimethoxysilane, trifluoropropyltrichlorosilane, and 3-chloropropyltrimethoxysilane may be used. When using, it is preferable to use epoxy acrylate type ultraviolet curable resin or urethane acrylate type ultraviolet curable resin. In addition, when using the silicon containing compound which has a vinyl group or an amino group in molecular terminal, such as vinyl trimethoxysilane, vinyl triethoxysilane, 3-aminopropyl trimethoxysilane, and 3-aminopropyl triethoxysilane, It is preferable to use polyester acrylate type ultraviolet curable resin.

Moreover, it is preferable to make thickness of a base layer into the value within 1-100 micrometers. The reason for this is that when the thickness of the base layer is less than 1 µm, it is difficult to improve the adhesion between the thin film metal layer and the substrate, or it is impossible to obtain a predetermined electrical resistance, light reflection characteristics, and also proper decorability and durability. Because there are cases. On the other hand, when the thickness of this thin film metal layer exceeds 100 micrometers, it will become difficult to use for a translucent mirror, or it may take too much manufacturing time, and manufacturing cost may become expensive.

Therefore, it is more preferable to make thickness of a thin film metal layer into the value within 0.1-50 micrometers range, and it is still more preferable to set it as the value within 0.5-10 micrometers range.

(2) reduction treatment device for metal ions

Next, the reduction processing apparatus 400 of metal ions used in the reduction treatment process of metal ions is demonstrated.

As the reduction treatment apparatus 400 for such metal ions, an apparatus as illustrated in FIG. 7 can be typically used.

That is, as the metal ion reduction treatment apparatus 400, a metal ion reduction treatment tank 401 capable of accommodating at least a treatment liquid (hereinafter, simply referred to as a treatment liquid) 402 containing a metal salt solution and a reducing agent. It is desirable to have In addition, it is preferable to equip the heater 403 in order to control the temperature of the processing liquid 402, as will be described later. Besides, although not shown, a pH meter for managing the processing liquid 402 under constant conditions, It is preferable to provide a viscometer, a stirring device, an ultrasonic vibration device, and the like.

On the other hand, it is preferable that such a metal ion reduction treatment apparatus 400 is provided in the following process of the surface treatment process in the manufacturing line of a thin film metal layer, as shown in FIG. It is also preferable to provide a simple and easy metal activation treatment step or cleaning step between the treatment step, or to provide another washing step, a pattern forming step, a resistor removal step, or the like as the next step.

Moreover, it is also preferable to use the spray gun 300 as shown in FIG. 8 as a modification of such a metal ion reduction processing apparatus 400. As shown in FIG.

That is, by using such a spray gun 300, not only the reduction of the metal ion reduction treatment apparatus can be reduced, but also the control of the metal ion reduction reaction can be easily controlled, or the treatment liquid 402 is sprayed only on a desired portion. It is also possible to selectively form a thin film metal layer.

Herein, the spray gun 300 will be described in more detail. As shown in FIG. 8, the gun main body 302 forms a pistol shape in which a body portion is disposed at an upper end of a handle, and the trigger portion 304 is formed in the body portion. ) Is attached. And the head part 303 is provided in the front-end | tip of the gun main body 302, The 1st discharge port J1 which ejects a metal salt solution in the front surface of this head part 303, and the 1st discharge port A second discharge port J2 for jetting the second liquid as a reducing agent arranged concentrically around J1, an air nozzle port J3 for jetting air, and a pure water nozzle port J4 for jetting pure water.

Therefore, the high pressure air is blown out from the air nozzle port through the air outlet P3 by opening of the on-off valve V3 of the trigger 304, and at this time, a part of the high pressure air flows into the cylinder chamber 319 and the needle valve 317 Retreat. As a result, the opening / closing valve V4 is opened to eject the pure water outflow passage P4 from the pure water inlet A4.

Therefore, from the spray gun 300, for example, the metal salt solution and the reducing agent are simultaneously flushed, and at the same time as or after the spraying, the pure water and the air are flushed to make the reduction reaction of the metal ions uniformly. There is a number.

On the other hand, as a modification of the spray gun 300 as shown in FIG. 8, the first spray gun for blowing out the metal salt solution and the reducing agent and the second spray gun for blowing out pure water and air are formed in the forming portion of the thin film metal layer. It is also preferable to use each.

Moreover, it is also preferable to use the spray unit 400 'as shown in FIG. 9 as a further modified example of such a metal ion reduction processing apparatus 400. As shown in FIG.

That is, in the process in which the workpiece | work W is conveyed to the direction shown by the arrow L by the conveyor 403, after spraying an activation process liquid or a cleaning liquid from the spray unit 406, 457, the 1st minute When a metal salt solution, for example, an aqueous solution of silver nitrate, is sprayed from the spray unit 454 used, and a reducing agent, for example, an aqueous solution of ammonia, is sprayed from the second spray unit 455, the surface of the workpiece W Silver nitrate in the silver nitrate solution is reduced, and silver precipitates. On the other hand, since the remaining liquid is washed and flowed by the pure water sprayed from the pure water spray units 453 and 456, the silver film is continuously formed on the surface of the workpiece W with a uniform layer thickness. Since the silver film formed by the reduction reaction of the metal ions is completely removed by the drying unit, yellowing due to moisture on the surface of the silver film is prevented, and high quality silver gloss can be obtained.

On the other hand, in the case of the spray unit 400 'shown in FIG. 9, the reducing liquid spray unit 451 or the pure water spray unit for spraying the surface of the workpiece W in an oblique direction while mixing with a reducing agent or pure water. 452 is installed. That is, it is because the thickness and the degree of reduction of the silver film are adjusted more accurately.

(3) metal salt solutions and reducing agents

Next, the treatment liquid used in the reduction treatment step of the metal ions, that is, the metal salt solution and the reducing agent will be described in detail.

First, as a kind of metal salt solution (including a metal complex solution) to be used, at least 1 type can be mentioned from gold nitrate, silver nitrate, copper nitrate, aluminum nitrate, nickel nitrate, and the like.

Moreover, it is preferable to make metal concentration in such a metal salt solution into the value within 0.001-3 mol / liter range.

The reason for this is that when the metal concentration is less than 0.001 mol / liter, the amount of precipitation of the metal may be remarkably lowered, which may lower the productivity of the thin film metal layer. On the other hand, when such a metal concentration exceeds 3 mol / liter, it becomes difficult to form a thin film metal layer uniformly on the surface of a base material, and productivity of a thin film metal layer may fall similarly. Therefore, it is more preferable to make the metal concentration in a metal salt solution into the value within 0.01-2.5 mol / liter, and it is still more preferable to set it as the value within 0.1-2 mol / liter.

On the other hand, as a reducing agent, formaldehyde, sodium borohydride, hydrazine, hydrazine compound, hydroquinone, L-ascorbic acid and salts thereof, pyrocatechol, ammonia, glucose, sodium hypophosphite, sulfite, formic acid, sodium sulfite anhydrous, L (+ ) One type single or two types or more combinations, such as tartaric acid and ammonium formate, are mentioned.

Among these reducing agents, since it is easy to control the reduction reaction of metal ions, L-ascorbic acid and its salt, ammonia, or L-ascorbic acid and its salt and pyrocatechol are used. It is more preferable.

Moreover, it is preferable to make the density | concentration of such a reducing agent into the value within 0.001-3 mol / liter range.

The reason for this is that when the concentration of such a reducing agent is less than 0.001 mol / liter, the amount of precipitation of the metal may be remarkably lowered, which may lower the productivity of the thin film metal layer. On the other hand, when the concentration of such a reducing agent exceeds 3 mol / liter, it is difficult to uniformly form the thin film metal layer on the surface of the substrate, which may lower the productivity of the thin film metal layer in the same manner.

Therefore, it is more preferable to set the concentration of the reducing agent to a value within the range of 0.01 to 2.5 mol / liter, and more preferably to a value within the range of 0.1 to 2 mol / liter.

(4) Reduction Treatment Condition of Metal Ions

Next, the reduction process conditions in the reduction process of a metal ion are demonstrated in detail.

First, it is preferable to make the temperature which performs the reduction process of metal ion, ie, the reduction process temperature of metal ion, be a value within the range of 0-80 degreeC.

The reason for this is that when such processing temperature is less than 0 ° C, it may take an excessive time to form a thin film metal layer having a predetermined thickness. On the other hand, when such a processing temperature exceeds 80 degreeC, it may become difficult to adjust the density | concentration of the reducing process liquid of a metal ion, and it may become difficult to form the thin film metal layer of uniform thickness on the surface of a base material.

Therefore, it is more preferable to make the process temperature at the time of the reduction process of metal ion into the value within the range of 5-50 degreeC, and it is still more preferable to set it as the value within the range of 10-30 degreeC.

In addition, although the reduction time of the metal ion per unit area (100 cm 2), that is, the reduction treatment time of the metal ions, depends also on the thickness of the desired thin film metal layer or the like, it is generally preferable to set the value within the range of 0.1 to 60 minutes. Do.

The reason for this is that when the processing time is less than 0.1 minutes, the thickness of the desired thin film metal layer may not be obtained stably. On the other hand, when this processing time exceeds 60 minutes, it will take too much manufacturing time, and manufacturing cost may become expensive.

Therefore, it is more preferable to make the processing time at the time of the reduction process of metal ion into the value within the range of 0.5-30 minutes, and it is still more preferable to set it as the value within the range of 1-10 minutes.

4. Inspection process

Next, as shown to FIG. 1 and FIG. 2, the inspection process of the thin film metal layer (including the front beta pattern) obtained in the reduction process of a metal ion is demonstrated.

First, in the manufacturing line of the thin film metal laminate 80 ″ including the thin film metal layer 86 shown in FIG. 7, before or after laminating the protective film 87 by the laminating apparatus 410, the thin film It is preferable to inspect the thickness, width, shape, or the like of the metal layer 86.

In such an inspection process, it is preferable to test whether the thickness of a thin film metal layer is a value in the range of 0.01-100 micrometers, for example.

The reason for this is that when the thickness of such a thin metal layer is less than 0.01 µm, predetermined electrical resistance, light reflection characteristics, and proper decorativeness and durability may not be obtained. On the other hand, when the thickness of such a thin film metal layer exceeds 100 micrometers, it may become difficult to use for a translucent mirror, or it may take too much manufacturing time, and manufacturing cost may become expensive.

Therefore, it is more preferable to make thickness of a thin film metal layer into the value within 0.1-50 micrometers range, and it is still more preferable to set it as the value within 0.5-10 micrometers range.

In addition, although the shape of a thin-film metal layer depends on a use, whether it is formed in various forms, such as a linear form, a spiral form, a spiral form, a curve form, a circular form, a loop form, or a three-dimensional structure in an inspection process, for example. It is preferable to check.

On the other hand, when a patterning process, a resist processing process, a plating process, etc. are provided after a metal ion reduction process, it is also preferable to check whether the aspect of the patterned thin-film metal layer, such as a character, a figure, a symbol, is good or bad. .

On the other hand, when performing an inspection process, it is also preferable to provide the process of forming a protective layer further, before laminating | stacking a protective film on the surface of a thin film metal layer as mentioned above.

The reason for this is that by forming a protective layer made of an ultraviolet curable resin, a thermosetting resin, a thermoplastic resin, an inorganic material, or the like on the surface of the thin film metal layer, the durability and scratch resistance of the thin film metal layer can be significantly improved. Moreover, by adding a coloring agent, electroconductive particle, etc. to the protective layer to form, it is because the decorative effect and external appearance of a thin film metal laminated body can be improved, and the resistance of a thin film metal layer can be stabilized more.

Here, as ultraviolet curable resin which comprises a protective layer, you may form as ultraviolet curable resin etc. similar to the base layer mentioned above, or ultraviolet curable resin etc. different from a base layer can also be used.

In addition, although the use etc. can also be determined about the thickness of a protective layer, it is preferable to set it as the value within 0.01-100 micrometers normally.

The reason for this is that when the thickness of the protective layer is less than 0.01 µm, the protective effect on the thin film metal layer may become insufficient or it may be difficult to form a uniform thickness. On the other hand, when the thickness of such a protective layer exceeds 100 micrometers, it is because the protective effect with respect to a thin film metal layer may become inadequate, or it may become difficult to form to a uniform thickness.

5. Object

According to the manufacturing method of the thin film metal laminate of the present invention, it can be developed by the manufacturing method of the object of various uses, but, for example, as a part of a play tool, an electric product, a vehicle, a mechanical part, a tool, a furniture, or an ornament It is preferable to form the thin film metal laminate of the present invention. For example, the amusement tool 500 provided with one part of the thin film metal laminated body as shown in FIG. 10 can be provided.

Moreover, it is also preferable to use a thin-film metal laminated body as a target object as a thin film metal pattern as a communication antenna, an antenna tag antenna, an electrical circuit wiring pattern, the electromagnetic shield metal pattern, or a decorative metal pattern.

Example 1

1. Fabrication of Thin Metal Laminates

A polypropylene film (10 cm in height X 10 cm in width X thickness 125 µm, referred to as PP in Table 1) was prepared as a substrate, and the surface of the polypropylene film was silicate using a surface modifying device shown in FIG. 4. The treatment was performed for 0.2 seconds per unit area (100 cm 2). On the other hand, as a fuel gas, a mixed gas containing a cartridge, which is compressed air containing 0.01 mol% of hexamethyldisilazane and 99.99 mol% of the remaining amount of propane gas, was used.

Subsequently, after apply | coating PES-B (SC) (made by Ishimart Japan Co., Ltd.) which is ultraviolet curable resin on the surface-treated base material, 300 mJ / cm <2> of ultraviolet-rays were irradiated, and the foundation layer of thickness 10micrometer was formed. did.

Subsequently, a 0.5-micrometer-thick silver layer was entirely formed on the formed base layer using the metal ion reduction processing apparatus shown in FIG. Thereafter, heat treatment was performed under conditions of 100 ° C. for 10 minutes using an oven, and further dried, a protective layer having a thickness of 10 μm made of the same ultraviolet curable resin as the base layer was formed on the formed silver layer. It was set as the thin film metal laminated body of 1.

2. Evaluation of Substrate and Thin Film Metal Layer

(1) volume resistivity

The volume resistivity (surface resistance) in the polypropylene film in the step of silicate treatment was measured based on JIS K6911. In addition, the volume resistivity of the polypropylene film before silicate treatment was measured similarly. The obtained results are shown in Table 1.

(2) wetness index

The wetness index in the polypropylene film of the silicate-treated step was measured using a standard solution. In addition, the wetness index of the polypropylene film before silicate treatment was measured similarly. The obtained results are shown in Table 1.

(3) adhesion

The board | substrate test based on JISK-5400 was performed, and the adhesiveness between the thin film metal layer and the polypropylene film was evaluated according to the following criteria. The obtained results are shown in Table 1.

(Double-circle): There is no peeling at all in 100 board scale test.

(Circle): In 100 board scale test, peeling water is 1-2 pieces.

(Triangle | delta): The peeling water is 3-10 pieces in 100 board scale tests.

X: In 100 board scale tests, peeling water is 11 or more.

EXAMPLES 2-6

In Examples 2-6, as shown in Table 1, except having changed the kind and surface treatment time of a silicon-containing compound, the thin film metal layer was formed on the polypropylene film like Example 1, respectively, and the adhesiveness of a thin film metal layer, etc. Was conducted. The obtained results are shown in Table 1.

EXAMPLES 7-10

In Examples 7-10, instead of the polypropylene film, except having used PET film (10 cm x 10 cm x thickness 125 micrometers, PET is called in Table 1), it was a thin film similarly to Examples 1-4, respectively. The PET film in which the metal layer was formed was created and evaluation of adhesiveness etc. was performed. The obtained results are shown in Table 1.

[Examples 11-14]

In Examples 11-14, it carried out similarly to Examples 1-4 except having used polycarbonate film (10cm in height X 10cm in width X thickness 2mm, PC in Table 1) instead of the polypropylene film. The polycarbonate film in which the thin film metal layer was formed was created, and adhesiveness etc. were evaluated. The obtained results are shown in Table 1.

[Examples 15-18]

In Examples 15-18, instead of the polypropylene film, except having used the low alkali glass board (10 cm in height X 10 cm in width x 2 mm in thickness, Table 1 is called glass), it carried out similarly to Examples 1-4, respectively. The glass plate in which the thin film metal layer was formed was created, and adhesiveness etc. were evaluated. The obtained results are shown in Table 1.

[Comparative Examples 1-4]

In Comparative Examples 1 to 4, after performing a plurality of activation treatments with tin and a parodydium without performing silicate treatment on the surfaces of the polypropylene film, PET film, polycarbonate film and low alkali glass plate, reduction treatment of metal ions A thin film metal layer was formed in the same manner as in Example 1, Example 7, Example 11, and Example 15, except that the adhesion and the like were evaluated. The obtained results are shown in Table 1.

* HMDN: Hexamethyldisilazane

＊ VTMS: Vinyltrimethoxysilane

* HMDN / ETA: Hexamethyldisilazane / ethanol

* HMDS: Hexamethyldisiloxane

As described above, according to the manufacturing method of the thin film metal laminate of the present invention, before the reduction treatment of metal ions on the substrate is performed to form the thin film metal layer, or before the base layer of the thin film metal layer is formed on the substrate. On the surface of the substrate, the flame of the fuel gas containing the silicon-containing compound is sprayed or the gaseous substance of the silicon-containing compound is sprayed through a heat source having a predetermined temperature or higher to have a uniform thickness and adhesiveness. A thin film metal laminate having this excellent thin film metal layer can be obtained.

Therefore, also about various base materials, such as glass, a ceramic, or a polyester resin, a polypropylene resin, etc., the thin film metal layer excellent in adhesiveness can be formed by a simple, easy, and quick manufacturing process.

In other words, it can be expected to provide a game device or an electric product that uses a thin film metal laminate as a target having a thin film metal laminate at a low price.

Claims (12)

In the manufacturing method of the thin film metal laminated body on a base material, the following processes (1)-(3) are included, The manufacturing method of the thin film metal laminated body characterized by the above-mentioned. (1) step of preparing the base material (2) A step of spraying a flame of a fuel gas containing a silicon-containing compound on the surface of the substrate or spraying a gaseous product of the silicon-containing compound through a heat source of 400 ° C or higher. (3) Process of Forming Thin Film Metal Layer by Reduction of Metal Ions The method for producing a thin film metal laminate according to claim 1, wherein the thickness of the thin film metal layer is set to a value within the range of 0.01 to 100 µm. The method for producing a thin film metal laminate according to claim 1 or 2, wherein the thin film metal layer contains at least one of gold, silver, copper, nickel, and aluminum as main components. The said thin film metal layer contains silver as a main component, The manufacturing method of the thin film metal laminated body of Claim 3 characterized by the above-mentioned. 2. The thin film metal laminate according to claim 1, wherein the thin film metal layer has a wetness index (measurement temperature of 25 ° C) on the surface of the substrate in the step (2) within a range of 40 to 80 dyn / cm. Way. The thin film metal layer production process according to claim 1, wherein the thin film metal layer has a volume resistivity of the surface of the substrate in the step (2) in a range of 1 × 10 ⁴ to 1 × 10 ¹⁰ Ω · cm. Way. The said thin film metal layer is further provided with the process of forming a (3 ') base layer between a process (2) and a process (3), The base layer between the said base material and a thin film metal layer Forming a thin film metal laminate. The thin film metal laminate according to claim 1, wherein the thin film metal layer has a spraying time of a flame or gaseous product in a range of 0.1 second to 100 seconds per unit area (100 cm 2). Way. The method for producing a thin film metal laminate according to claim 1, wherein the thin film metal layer contains at least one of a glass material, a polycarbonate resin, a polyolefin resin, a polyester resin, and a polyimide resin as the main component. . The thin film metal according to claim 1, wherein the thin film metal layer further includes (4) a step of forming a protective layer after the step (3), and forms a protective layer on the surface of the thin film metal layer. The manufacturing method of a laminated body. The said base layer, the protective layer, or either one is formed as an ultraviolet curable resin, The manufacturing method of the thin film metal laminated body of Claim 10 characterized by the above-mentioned. The thin film metal laminate according to claim 1, wherein the thin film metal layer forms the thin film metal laminate as part of a play tool, an electric appliance, a vehicle, a mechanical part, a tool, a furniture, or an ornament. Way.

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